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MICROCHEMICAL JOURNAL · 2024 · IF 4.9

Flexible plasmonic microneedle array-based SERS sensor for pH monitoring of skin interstitial fluid

Zhilong Chen,Yan Guo,Xinyue Gu,Xinyu Liu,Jingjing Zhang,Chunyuan Song,Lianhui Wang

Interstitial fluid (ISF) is a prevalent accessible and information-rich biofluid, and monitoring pH level of interstitial fluid plays a crucial role in the physiological health assessment. However, facile extraction of ISF and sensitive detection of pH is still a great challenge. Herein, a flexible plasmonic microneedle array (PMNA)-based SERS sensor was developed for facile and sensitive pH monitoring of skin ISF. The flexible microneedle arrays were fabricated by norland optical adhesive 65 (NOA65), and coated with pH-sensitive 4-Mercaptobenzoic acid (4-MBA)-labeled silver nanoparticles (Ag NPs) by electrostatic assembly. The proposed flexible PMNA-based SERS sensor has a good linear response in the pH range of 5 to 9 which covers the normal pH level in skin interstitial fluid. The ISF extracted from porcine skin was chosen as the test model, and the pH levels detected by the PMNA-based SERS sensors were well consistent with the theoretical results. Besides, the proposed flexible SERS sensors show good mechanical robustness, sensing stability, and biocompatibility before and after skin insertion, which can be a potential analytical tool for practical detection of pH levels in ISF and provide technical support for SERS-based wearable biosensing.

CAS / MDL: 26062-79-3
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COLLOIDS AND SURFACES A-PHYSICOCHEMICAL AND ENGINEERING ASPECTS · 2024 · IF 4.9

Functionalization Ti3C2Tx as highly sensitive and selective SERS substrate by reduction rapid synthesis strategy

Ruoyu Zhang,Shan Li,Baoru Liu,Xinyu Yang,Weijun Kang,Lianfeng Ai

In this study, we designed and prepared a novel, stable, and sensitive membrane-based surface-enhanced Raman scattering (SERS) substrate based on the synergistic interaction of two-dimensional MXene material Ti 3 C 2 Tx and silver nanoparticles (AgNPs). Using this AgNPs/Ti 3 C 2 Tx active substrate, a rapid SERS method for determination of paraquat residues in vegetables and fruits was developed. The AgNPs/Ti 3 C 2 Tx films were formed by dropping AgNO 3 solution onto the film and drying, which was synthesized by wet chemical method , and then filtered into an exfoliated Ti 3 C 2 Tx film. The Ti 3 C 2 Tx film can not only effectively enrich analytes, but also provide charge transfer resonance enhancement. The homogeneous AgNPs particle size of 40–120 nm on the substrate surface of Ti 3 C 2 Tx can effectively enhance the Raman signal intensity, and the enhancement factor of methylene blue can reach 10 5 . The detection limit of the detection method for paraquat in 9 fruit and vegetable matrices was lower than 3.0 μg/kg, and the limit of quantification was lower than 12 μg/kg. The results suggest that AgNPs/Ti 3 C 2 Tx platform could be used as a sensitive and reliable for food safety analysis based on SERS method.

CAS / MDL: 7789-24-4
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CHEMICAL ENGINEERING JOURNAL · 2025 · IF 13.2

Diagnosis of Early opioids addiction by label-free serum SERS fingerprints with machine learning

Yunfan Chen,Haitao Li,Jing Shi,Jiajun Cheng,Zhuolu Song,Xinyue Zhang,Xinnan Li,Jialin Zhuang,Qi An,Zeguo Feng,Long Wang

Opioids addiction has been steadily rising worldwide, posing serious medical and social challenges. However, there is currently no gold standard for diagnosing opioid addiction for the lack of a specific biomarker. Surface-enhanced Raman scattering (SERS) is widely employed in screening complex components for its capacity to present fingerprint features in the spectra. However, it remains challenging to test blood samples to diagnose diseases without biomarkers using SERS. Here, we introduce a machine learning (ML) assisted, SERS-based platform for analysis of serum of addiction mouse, enabling the diagnosis of morphine and fentanyl addiction. We identify that the proper ligand choice during preparation of the SERS substrate is essential for obtaining clear signal from blood samples. Among several capping ligands, only sodium citrate leads to successful SERS substrate fabrication being able to test blood samples. The critical role of the citrate ligand to promote adsorption and charge transfer between the substrate and the biomolecule of interest is demonstrated. Accuracy rates up to 100% and 87% are achieved for morphine addiction and fentanyl addiction analyses. The present work paves a new way achieving clinical label-free serum diagnosis of morphine and fentanyl addiction by SERS with machine learning, showing its potential for fast-screening of diseases without a clear biomarker.

CAS / MDL: 16940-66-2
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Journal of Physical Chemistry C · 2024 · IF 3.3

AI Algorithm-Assisted SERS Detection of Levothyroxine Sodium in Urine by an Optoplasmonic Film

Qi Liu,Wenrou Yu,Anping Liu,Zhaoxian Chen,Xuliang Xia,Yingzhou Huang,Haiyang Shi

By harnessing the capture of target molecules at the metal surface via a highly confined electromagnetic field induced by surface plasmons, surface-enhanced Raman spectroscopy (SERS) has emerged as a sensitive technique for spectral analysis. However, the precise identification of biomarkers in urine using SERS remains a formidable challenge due to the low concentration of biomarkers and the complex nature of the urine composition. In this investigation, we developed an optoplasmonic film SERS substrate comprising silver nanowires (AgNWs) and silicon dioxide (SiO2) to tackle this issue. The AgNWs produce robust SERS signals, while SiO2 enhances laser focusing, facilitating the efficient detection of levothyroxine sodium (LS) in urine with an ultralow detection limit of 1 × 10–9 M. Leveraging artificial intelligence (AI) algorithms, this optoplasmonic substrate achieved precise LS identification in urine with a remarkable accuracy rate. This pioneering substrate holds substantial promise for the noninvasive, swift detection of target molecules in biofluids, heralding advancements in disease diagnostics and health monitoring.

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Journal of Physical Chemistry C · 2024 · IF 3.3

Amoxicillin-Induced Purine Molecules Were Used as Bacterial Markers for SERS Detection and Recognition

Yan Hong,Zhicai Meng,Cong Han,Ronglu Dong,Dongyue Lin,Liangbao Yang

The amalgamation of surface-enhanced Raman spectroscopy (SERS) and machine learning (ML) presents a discerning capability to differentiate among a diverse spectrum of bacterial strains. However, addressing the challenge of achieving expeditious and robust bacterial detection remains a prominent focal point. This study delineates a comprehensive bacterial classification and identification methodology grounded in the amoxicillin response, which effectively categorizes bacteria utilizing SERS and ML within a time frame of less than 20 min. The bacterial specimens are subjected to pharmacological stimulation, inducing the release of purine molecules that are integral to metabolic processes. Capitalizing on the preferential entry of these molecules into SERS hot spots over the bacteria themselves facilitates the consistent acquisition of stable SERS signals. Experimental evidence demonstrates that the interaction of S. aureus, E. coli, S. epidermidis, C. albicans, and K. pneumoniae with amoxicillin contributes to an enhancement in the stability and signal intensity of bacterial SERS. Utilizing a random forest (RF) model on pure bacterial samples yields an exemplary classification accuracy of 99%. Furthermore, the application of three distinct models, support vector machine (SVM), RF, and CNN-LSTM-Attention (CLA) in the analysis of clinical samples culminates in final classification accuracies of 92%, 87%, and 96%, respectively. This approach establishes a rapid, straightforward, and stable classification methodology for SERS-based bacterial detection, demonstrating significant potential for clinical diagnostic applications.

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Analytical Methods · 2024 ·Vol. 16 ·期 45 ·7683-7688 · IF 2.7

A sensitive SERS-based assay technique for accurate detection of foodborne pathogens without interference

Xiangru Bai,Wei Luo,Wenyu Zhou,Wei Chen,Xinling Guo,Aiguo Shen,Jiming Hu

The accurate and sensitive detection of foodborne pathogens is critical for timely food quality supervision and human health. To address this issue, herein, we developed a simple and novel surface-enhanced Raman scattering (SERS) assay using p-mercaptobenzoic acid (MBN)-modified gold nanoparticles (Au NPs) and magnetic beads for interference-free detection of Escherichia coli (E. coli). This assay technique cleverly reduced silver ions (Ag+) on the surface of E. coli (bacteria@Ag NPs), and the functionalized magnetic beads (capture probes) captured and enriched bacteria@Ag NPs, forming the structure of the capture probes–bacteria@Ag NPs. Then, the capture probes–bacteria@Ag NPs were dissolved in the acidic medium, and the Ag NPs on the surface of E. coli was converted to Ag+ again. Due to the special coordination between Ag+ and MBN-modified Au NPs (functionalized Au NPs), the SERS intensity of MBN exhibited a positive correlation with the E. coli concentration, and the SERS detection assay of E. coli was established. The signal of the functionalized Au NPs located at 2228 cm−1 perfectly avoided the spectral overlap with coexisting materials in the Raman fingerprint region, which ensured the accuracy of the technique. The controlled aggregation of the functionalized Au NPs ensured the reproducibility and reliability of the detection system; the emergence of MBs greatly reduced the reaction time and made sure the operation was rapid, simple and portable. The limit of detection (LOD) for E. coli was as low as 10 cfu mL−1, and the detection assay was successfully applied for the detection of E. coli in bottled water and milk. As a sensitive and accurate analytical technique for the detection of pathogens, this SERS-based method has great potential to be applied in the field of food safety.

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Small · 2024 · IF 13

Magnetic Micromotors with Spiky Gold Nanoshells as SERS Sensors for Thiram and Bacteria Detection

Tao Yang,Jianping Zhou,Yongkang Wang,Ben Fan,Jing Qiao,Lixiang Chen,Xiaoyu Wang,Lingxiang Guo,Hong Yang,Quan Li

Surface-enhanced Raman scattering (SERS) is widely used in all kinds of detection due to its ultrahigh sensitivity and selectivity. Micromotors, when used as SERS sensors, or the so-called “hotspots on the fly”, can combine both controlled mobility and SERS sensing capacity, and are ideal for versatile in situ detection. In this work, mobile SERS sensors are successfully fabricated by growing gold nanospikes onto magnetic microsphere surfaces. These mobile micromotors can act as normal SERS sensors, characterized by the trace detection of thiram, a highly toxic fungicide. The detection limit can reach 0.1 n M , as good as most other noble metal deposited substrates. With significant magnetic gradient forces, separation of pathogenic bacteria from bulk solution is achieved once these magnetic micromotors bind with bacterial cells. Manipulated propulsion of micromotors, on the other hand, enables them to approach and contact pathogenic bacterial cells on command and further acquire Raman spectra under a controlled degree of contact, a capability never seen with passive sensors. The robotic SERS sensors have demonstrated unique sensing characteristics with controlled manipulations along with discriminative detection between bacterial species.

CAS / MDL: 79-06-1
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Small · 2015 ·Vol. 11 ·期 18 ·2200-2208 · IF 8.368

Selective Capture and Quick Detection of Targeting Cells with SERS-Coding Microsphere Suspension Chip

Dian Li,Yuting Zhang,Ruimin Li,Jia Guo,Changchun Wang,Chuanbing Tang

Circulating tumor cells (CTCs) captured from blood fluid represent recurrent cancers and metastatic lesions to monitor the situation of cancers. We develop surface-enhanced Raman scattering (SERS)-coding microsphere suspension chip as a new strategy for fast and efficient capture, recovery, and detection of targeting cancer cells. Using HeLa cells as model CTCs, we first utilize folate as a recognition molecule to be immobilized in magnetic composite microspheres for capturing HeLa cells and attaining high capturing efficacy (up to 95%). After capturing cells, the composite microsphere, which utilizes a disulfide bond as crosslinker in the polymer shell and as a spacer for linking folate, can recycle 90% cells within 20 min eluted by glutathion solution. Taking advantage of the SERS with fingerprint features, we characterize captured/recovered cells with the unique signal of report-molecule 4-aminothiophenol through introducing the SERS-coding microsphere suspension chip to CTCs. Finally, the exploratory experiment of sieving cells shows that the magnetic composite microspheres can selectively capture the HeLa cells from samples of mixed cells, indicating that these magnetic composite microspheres have potential in real blood samples for capturing CTCs.

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PHYSICAL CHEMISTRY CHEMICAL PHYSICS · 2024 ·Vol. 26 ·期 22 ·16287-16295 · IF 2.9

Plasma amplifiers: multiscale light-enhanced uniform SERS composite substrates for breaking through resonance limitations

Jinqiao Lu,Fen Yang,Zhen Wang,Jie Huang,Shangzhong Jin,Pei Liang

A phenomenon known as plasmon resonance constitutes a unique optical effect that can induce an enhancement in localized electromagnetic fields, resulting in a substantial increase in the electromagnetic field intensity surrounding metallic nanostructures. In this work, the coupling effect of excitation of surface plasmon polaritons and local surface plasmons in nanoparticles is deeply studied under the background of nanoparticles/one-dimension grating composite structures through grating matching. By employing finite-difference time-domain simulations as our methodological approach, we discern gratings with a periodicity of 1.5 μm support surface plasmon bound states between the gratings. Furthermore, the modulation of SPs along the vertical sidewalls of the grating due to standing wave effects exhibits oscillatory behavior with varying grating heights. Experimental results obtained from the nanoparticle/grating composite SERS substrate validate theoretical predictions, demonstrating higher enhanced Raman signals at 633 nm compared to 532 nm. Remarkably, this structure exhibits good performance, with R6G detection sensitivity down to concentrations as low as 10−10 M and mapping achieving a relative standard deviation of 7.79%, underscoring its uniformity and capability of electromagnetic field enhancement.

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SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY · 2024 · IF 4.3

Simple, ultrasensitive detection of superoxide anion radical mutations in melanoma mice with SERS microneedles

Miao He,Lili Jin,Feng Wang,Xin Wang,Yanli You,Hongyan He

Elevated levels of superoxide anion radicals (O 2 ·− ) have been implicated in the pathogenesis of a variety of diseases, such as cancer, inflammatory diseases and autoimmune diseases. To determine the O 2 ·- concentration for assisting disease detection, a method based on surface-enhanced Raman scattering (SERS) combined with transparent polymer microneedles has been developed. Photocrosslinked NOA61 is used to prepare microneedles with sulfhydryl group, which can contribute to anchor gold nanoparticles (Au NPs) functionalized by p-mercaptobenzoic acid (PATP). This work successfully constructed SERS microneedles for in situ detection. A REDOX reaction occurred between PATP and O 2 ·- , resulting in the formation of dimethylaminoborane (DMAB) and a subsequent change in Raman signal. Based on the quantitative relationship between the change of peak area ratio at 1042 cm −1 and 1077 cm −1 and the concentration change of O 2 ·- , a standard curve with a linear range of 0–480 ng/mL was constructed. The SERS microneedles were effectively employed to track melanoma progression in mice, establishing a fundamental correlation between O2·- concentration and melanoma stage, as confirmed by ELISA. The benefits of this approach, including convenience, in situ applicability, and low cost, are anticipated to offer novel insights for non-invasive in situ detection, potentially enhancing disease monitoring and diagnosis.

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SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY · 2025 · IF 4.6

Small Au nanoparticles to be modified with decavanadate for sensitive and stable SERS detection

Borong Yu,Jiawei Zhao,Jiayi Zhao,Zhengguo Lin,Chengxiang Zhao,Mengqi Tian,Fangwei Han,Yuanyuan Ma,Zhangang Han

Surface enhanced Raman spectroscopy (SERS) has been a powerful vibrational optical spectroscopic technique for trace determination. And the application and promotion of SERS technology are closely related to plasmonic substrates. To combine the distinct electronic properties of polyoxovanadates with the plasmonic properties of Au NPs, the small cit-Au NPs (reduced by sodium citrate) was modified with decavanadate (V 10 ) via ligand displacement. The structure of V 10 was controlled by pH adjustment. X-ray photoelectron spectroscopy (XPS) and SERS were introduced for studying interactions of V 10 with the surface of Au NPs. Compared with cit-Au NPs, V 10 -Au NPs owned higher absolute value of zeta potential and presented greater stability in CH 3 OH/H 2 O (V/V = 1:10) solvent environment. Even after 60 min of soaking, the V 10 -Au NPs still exhibited a typical coffee ring effect during the evaporation process with SERS enhancement. The stability of V 10 -Au NPs (in a solution with pH 4.8) was tested over a period of 5 days to indicate their ability to maintain SERS activity. Moreover, the V 10 -Au NPs also showed great sensitivity for cationic dye molecules and antibiotics, and the detection levels could be as low as μg⋅L −1 . This study lays the foundation for the screening low-concentration cations in mixed solutions and monitoring the morphological changes of polyoxometalates during their application via SERS technology.

CAS / MDL: 7803-55-6 68649-12-7
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ANALYTICAL CHEMISTRY · 2025 · IF 6.7

Smart and Noninvasive SERS Immunosensors for Monitoring Dynamic Expression of Cytokines during Cell Pyroptosis

Chenyu Zhang,Zutao Chen,Guohua Qi,Yu Tian,Xiongjian Zheng,Xingkang Diao,Jiao Kong,Xingkai Ju,Jing Li,Shaojun Dong,Yongdong Jin

Accompanying the occurrence of inflammatory reaction to release cytokines, pyroptosis can activate an immune response for resistance against cancer. Consequently, elevated levels of cytokines released by cancer cells are highly correlated with the effectiveness of cancer treatment. Herein, a noninvasive surface-enhanced Raman spectroscopy (SERS) immunosensor was developed to sensitively and specifically measure the tumor necrosis factor-α (TNF-α), a proinflammatory cytokine, during the cell pyroptosis process. The sandwiched structure of the sensor is functionalized with a TNF-α binding antibody for detecting TNF-α at concentrations as low as 1 pg/mL. Importantly, electrical stimulation (ES) can fleetly trigger cancer cell pyroptosis to induce the overexpression of receptor interacting protein 3 (RIP3), which is a significant protein that regulates the inflammatory response. The overexpression of RIP3 can activate caspase-1 to promote the upregulation of cytokine levels. Notably, the cytokine levels of TNF-α released from cancer cells (MCF-7 cells) were apparently higher than those of normal cells (MCF-10A cells) during pyroptosis detected by the SERS immunosensors. Due to its obvious superiorities of simple fabrication and fast readout without sample pretreatment, the developed SERS platform has a potential application value for diagnosis and treatment of cancer.

CAS / MDL: 30525-89-4 9002-93-1
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